CN101054007A - Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates - Google Patents

Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates Download PDF

Info

Publication number
CN101054007A
CN101054007A CN 200610074600 CN200610074600A CN101054007A CN 101054007 A CN101054007 A CN 101054007A CN 200610074600 CN200610074600 CN 200610074600 CN 200610074600 A CN200610074600 A CN 200610074600A CN 101054007 A CN101054007 A CN 101054007A
Authority
CN
China
Prior art keywords
organic
film
inorganic film
inorganic
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 200610074600
Other languages
Chinese (zh)
Inventor
曹荣
高水英
李涛海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Institute of Research on the Structure of Matter of CAS
Original Assignee
Fujian Institute of Research on the Structure of Matter of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Institute of Research on the Structure of Matter of CAS filed Critical Fujian Institute of Research on the Structure of Matter of CAS
Priority to CN 200610074600 priority Critical patent/CN101054007A/en
Publication of CN101054007A publication Critical patent/CN101054007A/en
Pending legal-status Critical Current

Links

Landscapes

  • Laminated Bodies (AREA)

Abstract

An organic-inorganic membrane is self-assembly by organic dye and polyoxometallate and relates to an organic-inorganic membrane and the manufacturing method of the same. The membrane is manufactured by XW12(x=B, Si, P)or[M4II(H20)(PW9O34)2]10-(M=Co, Cu, Zn, Mn)and organic dye of Bismarck Brown Y, Azure A and Basic Blue3 by means of a layer upon layer self-assembly method. The membrane has the abundant chemical properties of polyoxometallate and has the properties of organic dye, and has potential application prospect in the aspects of chemical modification electrode and optical material.

Description

The organic and inorganic composite membrane of organic dyestuff and polyoxometallate self assembly
Technical field
The present invention relates to a kind of organic, inorganic composite film, relate in particular to the organic and inorganic composite membrane of a kind of organic dyestuff and polyoxometallate self assembly.
Background technology
Along with the develop rapidly of electronics and information science, people are developed apace to the research of material science, and this also just requires device to need microminiaturization, multifunction, integrated etc.Yet single species is formed the material of preparation and is difficult to satisfy simultaneously multiple needs.And the organic and inorganic composite membrane carries out combination with organic matter and inorganic matter on molecular level, makes material promptly have the rigid nature that organic flexible characteristic has inorganic matter again.At present, the organic and inorganic composite membrane is owing to it has potential application and obtained extensive studies industrial.Organic dye molecule makes it have potential technology at nonlinear optics, holography, data storage and Organic Light Emitting Diode and uses owing to have the structural system of conjugation.Such as, organic dyestuff owing to very strong absorption is arranged at visible region, thereby the semi-conducting material that can sensitization has big bandwidth, this just makes them be applied in transform light energy.The cd-recordable (CD-R) that also has us to use, its recording layer mainly is that kind organic dye film is made.Polyoxometallate (Polyoxometalates, POMs), inorganic metal oxygen cluster compound as a quasi-representative has abundant structures, chemistry and performance physically, thereby it has important theoretical research value and wide application prospect in fields such as catalysis, medicine and materials chemistries.Yet the preparation of their these its films of potentiality application need.Self-assembly method is a kind of effective ways of constructing the organic and inorganic composite membrane layer by layer.This method alternately is immersed in anion and the cationic solution.Utilize self-assembly method layer by layer, as inorganic anion, simple chain organic matter is a cation, has prepared the organic self-assembled supermolecular film of a series of POMs-with POMs.But as far as we know, people are also relative less to the composite membrane research of organic dyestuff and polyoxometallate at present.In general, water miscible organic dyestuff all is to have the charged dye molecule of aromatic rings, and polyoxometallate is the big inorganic clusters compound that a class has negative electrical charge.
Summary of the invention
The objective of the invention is to prepare a kind of organic dyestuff and polyoxometallate and the organic and inorganic composite membrane.
The present invention is achieved by the following technical solutions, and method is as follows: at first, quartz glass plate or glass-carbon electrode are carried out cleaning treatment, clean with distilled water, nitrogen dries up; Quartz glass plate after will handling then or glass-carbon electrode are immersed in cationization in polymine (PEI) solution; Again 20min in solution that alternately is immersed in polyoxometallate (POMs) through the substrate of cationization and the organic dyestuff solution, each immerses and cleans with distilled water after step is taken out, nitrogen dries up, and this step that circulates can make the organic dyestuff-polyoxometallate composite membrane of the different numbers of plies.
The polyoxometallate that the present invention adopts is XW 12O 40(X=B, Si, P) or [M of Transition metal substituted 4II (H 2O) 2(PW 9O 34) 2] 10-u(M=Co, Cu, Zn, Mn).
Three kinds of cation organic dyestuff that the present invention adopts are Bismarck brown Y (BBY), Azure A (AzA), and its structural formula of Basic Blue 3 (BB3) is as follows.
Figure A20061007460000041
Figure A20061007460000051
Organic dyestuff-polyoxometallate the composite membrane of the present invention's preparation is synthetic first.This composite membrane promptly has the abundant chemical property of polyoxometallate, has the characteristics of organic dyestuff again, is a kind of compound film with multifunction; Especially use organic dyestuff as organic cation, this composite membrane is expected to be applied on optical material.
The specific embodiment
Embodiment 1:(BW 12/ BBY) nThe preparation of multilayer organic and inorganic film
At first, quartz plate is cleaned: quartz glass plate is placed 98%H 2SO 4With 30%H 2O 2(7: in 80 ℃ of following impregnation process 40min, take out the back and clean in mixed liquor 3v/v) with distilled water; Immerse H again 2O: H 2O 2: NH 3=5: in 80 ℃ of following impregnation process 20min, take out the back and clean with distilled water in the mixed liquor of 1: 1 (v/v/v), nitrogen dries up, and promptly obtains the stand-by substrate of film forming.
Again substrate is carried out the PEI cationization: will immerse in the polymine PEI solution of 10mg/mL through the substrate of aforementioned processing program and place 20min, and take out the back and clean with distilled water, nitrogen dries up.
And then, alternately immerse 4.0 * 10 substrate through the PEI cationization -2The BW of M 12Solution and 1.0 * 10 -3In the M BBY solution, place 20min respectively, each immerses and cleans with distilled water after step is taken out, and nitrogen dries up; The above step of repetitive cycling can make required (BW 12/ BBY) nMultilayer organic and inorganic film.
The uv-vis spectra of film is characterized in the ultraviolet-visual spectrometer of the Lambda-35 type of U.S. PerkinElmer company production.Uv-vis spectra shows that the film of preparation in the increase linear along with the increase of the number of plies of the absorbance of wavelength 257nm and the BW12/BBY of 470nm place, illustrates that the film of preparation has the good homogeneous growth property.
The AFM of film is characterized in U.S. NanoScope IIIa, and (Digital Instruments Inc.), adopts the pattern, sweep limits 1.0 * 1.0 μ m of rapping 2Characterization result shows that film surface is all very even, (BW 12/ BBY) 4(BW 12/ BBY) 4-BW 12Roughness of film (RMS) is respectively 1.532nm and 2.022nm.Film (BW 12/ BBY) 4-BW 12Surface roughness is than (BW 12/ BBY) 4The successful preparation of film is described greatly.
Embodiment 2:([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BBY) nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10 -3[the Co of M 4 II(H 2O) 2(PW 9O 34) 2] 10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 250nm and the [Co of 468nm place 4 II(H 2O) 2(PW 9O 34) 2] 10-The increase that the absorbance of/BBY is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.AFM characterization result explanation film surface is all very even, ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BBY) 4([Co 4II (H 2O) 2(PW 9O 34) 2] 10-/ BBY) 4-[Co 4 II(H 2O) 2(PW 9O 34) 2] 10-Roughness of film (RMS) is respectively 0.971nm, 1.694nm (1.0 * 1.0 μ m 2Film ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BBY) 4Surface roughness is than ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BBY) 4-[Co 4 II(H 2O) 2(PW 9O 34) 2] 10-The successful preparation of film is described greatly.
Embodiment 3:(BW 12/ AzA) nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion organic dyestuff of substrate adopts 0.5 * 10 -3M AzA solution.
Uv-vis spectra shows that the film of preparation is at wavelength 250nm, 285nm and the BW of 594nm place 12The increase that the absorbance of/AzA is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.
The AFM characterization result explanation film surface of film is all very even, (BW 12/ AzA) 4(BW 12/ AzA) 4-BW 12Roughness of film (RMS) is respectively 1.324nm, 1.715nm.Film (BW 12/ AzA) 4-BW 12Surface roughness is than (BW 12/ AzA) 4The successful preparation of film is described greatly.
Embodiment 4:([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 3.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10 -3[the Co of M 4 II(H 2O) 2(PW 9O 34) 2] 10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 247nm, 285nm and the [Co of 584nm place 4II (H 2O) 2(PW 9O 34) 2] 10-The increase that the absorbance of/AzA is linear along with the increase of the number of plies illustrates that the film of preparation has the good homogeneous growth property.AFM characterization result explanation film surface is all very even, ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) 4([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) 4-[Co 4 II(H 2O) 2(PW 9O 34) 2] 10-Roughness of film (RMS) is respectively 3.373nm, 4.845nm.Film ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) 4Surface roughness is than ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) 4-[Co 4 II(H 2O) 2(PW 9O 34) 2] 10-The successful preparation of film is described greatly.
Embodiment 5:(BW 12/ BB3) nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 1.Wherein the immersion organic dyestuff of substrate adopts 0.5 * 10 -3M BB3 solution.
Uv-vis spectra shows that the film of preparation is at wavelength 260nm, 615nm and the BW of 670nm place 12The absorbance of/BB3 increases along with the increase of the number of plies, illustrates that film successfully prepares.
The AFM characterization result explanation film surface of film is all very even, (BW 12/ BB3) 4-BW 12Roughness of film (RMS) is 3.154nm.
Embodiment 6:([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BB3) nThe preparation of multilayer organic and inorganic film
Synthesis step and testing procedure are with reference to embodiment 5.Wherein the immersion solution of the substrate of PEI cationization adopts 5.0 * 10 -3[the Co of M 4 II(H 2O) 2(PW 9O 34) 2] 10-Solution.
Uv-vis spectra shows that the film of preparation is at wavelength 255nm, 615nm and the [Co of 665nm place 4 II(H 2O) 2(PW 9O 34) 2] 10-The absorbance of/BB3 increases along with the increase of the number of plies, illustrates that film successfully prepares.
The AFM characterization result explanation film surface of film is all very even, ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BB3) 4-[Co 4II (H 2O) 2(PW 9O 34) 2] 10-Roughness of film (RMS) is 3.154nm.

Claims (8)

1. the organic and inorganic film of organic dyestuff and polyoxometallate self assembly, it is characterized in that: this film is by organic dyestuff Bismarck Brown Y or Azure A or Basic Blue 3 and polyoxometallate XW 12(X=B, Si P) form.
2. organic and inorganic film as claimed in claim 1 is characterized in that: described XW 12By [M 4 II(H 2O) 2(PW 9O 34) 2] 10-(Zn Mn) replaces for M=Co, Cu.
3. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW 12/ BBY) nMultilayer organic and inorganic film.
4. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BBY) nMultilayer organic and inorganic film.
5. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW 12/ AzA) nMultilayer organic and inorganic film.
6. organic and inorganic film as claimed in claim 1 is characterized in that: this organic and inorganic film is (BW 12/ BB3) nMultilayer organic and inorganic film.
7. organic and inorganic film as claimed in claim 2 is characterized in that: this organic and inorganic film is ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ AzA) nMultilayer organic and inorganic film.
8. organic and inorganic film as claimed in claim 2 is characterized in that: this organic and inorganic film is ([Co 4 II(H 2O) 2(PW 9O 34) 2] 10-/ BB3) nMultilayer organic and inorganic film.
CN 200610074600 2006-04-11 2006-04-11 Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates Pending CN101054007A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200610074600 CN101054007A (en) 2006-04-11 2006-04-11 Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200610074600 CN101054007A (en) 2006-04-11 2006-04-11 Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates

Publications (1)

Publication Number Publication Date
CN101054007A true CN101054007A (en) 2007-10-17

Family

ID=38794134

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200610074600 Pending CN101054007A (en) 2006-04-11 2006-04-11 Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates

Country Status (1)

Country Link
CN (1) CN101054007A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112820A (en) * 2013-04-18 2014-10-22 东北师范大学 Polyoxometallate-based composite film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112820A (en) * 2013-04-18 2014-10-22 东北师范大学 Polyoxometallate-based composite film
CN104112820B (en) * 2013-04-18 2017-08-25 东北师范大学 A kind of laminated film based on polyoxometallate

Similar Documents

Publication Publication Date Title
Knoll Self-assembled microstructures at interfaces
Liang et al. Covalent layer‐by‐layer assembly of conjugated polymers and CdSe nanoparticles: multilayer structure and photovoltaic properties
Katz Multilayer deposition of novel organophosphonates with zirconium (IV)
Huck et al. Patterned polymer multilayers as etch resists
Kawai et al. Molecular orientation in LB films of azobenzene-containing long-chain fatty acids and their barium salts studied by FT-IR transmission and reflection-absorption spectroscopy
US20100051967A1 (en) Absorbing film
JP5024979B2 (en) Photoelectric device having multilayered organic thin film, method for producing the same, and solar cell
Genzer et al. Fabricating two‐dimensional molecular gradients via asymmetric deformation of uniformly‐coated elastomer sheets
Sugi Molecular engineering in Japan—A prospect of research on Langmuir-Blodgett films
CN101054007A (en) Automatic assembly organic-inorganic composite film for organic dyestuff and polyoxometalates
CN101879795B (en) Phthalocyanine/TiO2 ordered film and preparation method thereof
CA1328786C (en) Layer elements and their production
CN1903561A (en) Self-assembling organic-inorganic composite film made of various kinds of metal oxy-acidic salts and thia-calicene aromatic hydrocarbon
Potlog et al. Physical–Chemical Properties of Self-Assembled Structures in Solution of Zinc Phthalocyanine and Bis-3-pentyl-PTCDI Derivative
Fu et al. Molecular orientation of the silver tetraneopentoxyphthalocyanine and stearic acid mixed Langmuir-Blodgett film and its chemical and electrochemical behavior
KR100614414B1 (en) Silica nanoparticles capped conductive polymers and manufacture method therefor
Kato et al. Molecularly thin polymer films that function to enhance charge injection efficiency in organic light-emitting diodes
KR100586869B1 (en) The conductive and transparent substrate with thin layers of the high molecular compound polymers by self-assembly and the preparing method of it
Liu et al. Highly Luminescent Chiral Double π-Helical Nanoribbons
Advincula et al. Supramolecular thin film architectures for photonic applications
CN1282976C (en) Method for producing graded self-assembling ultrathin conductive membrane containing gold nano-particles
US7782408B2 (en) 3-D molecular assembly and its applications for molecular display and moletronics
Fu et al. 1NO. NO.~
CN1903701A (en) Multi oxometallate and amination calixarene self assembled organic-inorganic composite film
CN115849726A (en) Surface-enhanced Raman scattering composite substrate and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20071017